Fuel 86 (2007) 3–16

www.fuelfirst.com

Mechanical/thermal dewatering of lignite. Part 3: Physical

properties and pore structure of MTE product coals
a,* b,1
Christian Bergins , Janine Hulston , Karl Strauss a, Alan L. Chaffee b

a
Energy Process Engineering and Fluid Mechanics, Department of Biochemical and Chemical Engineering,
University of Dortmund, 44221 Dortmund, Germany
b
CRC for Clean Power from Lignite, School of Chemistry, Monash University, Clayton, Vic. 3800, Australia

Received 17 May 2006; received in revised form 26 June 2006; accepted 27 June 2006
Available online 7 August 2006

Abstract

The mechanical thermal dewatering (MTE) process has been shown to effectively dewater high moisture content low rank coals via the
application of mechanical force at elevated temperatures.
Using mercury intrusion porosimetry (MIP) as an investigative tool, this study examines how MTE processing conditions, such as tem-
perature and pressure, affect the compressibility, pore size distribution, apparent (skeletal) density and shrinkage behaviour of three low
rank coals sourced from Australia, Greece and Germany. As both pore filling and sample compression occurred at high mercury intrusion
pressures, all MIP data were corrected for compression effects by using compressibility values derived from mercury extrusion data.
The MTE process is shown to produce a low porosity coal, which, depending upon the processing conditions used, undergoes further
shrinkage upon oven drying at 105 C. An increase in MTE temperature (above about 85 C) led to an increase in mesopore volume,
which is caused by a hardening of the coal structure, leading to pore volume retention and a consequent reduction in percent shrinkage
on oven drying. The increase in measured mesopore volume is also associated with an increase in measured surface area.
The reverse trend is seen with increasing MTE pressure, where both the macro and mesopore volume decrease with pressure, causing
the percent shrinkage to increase accordingly. This effect may be due to an increase in capillary forces caused by a decrease in the average
pore diameter. The percent shrinkage increased up to a pore volume of about 0.1 cm3/g, beyond which no further reduction in pore vol-
ume was achieved. The decrease in mesopore volume is also associated with a decrease in measured surface area.
Compressibility values derived from mercury extrusion data show that the MTE process has little impact on the network strength of
the skeletal network structure of all three coals investigated. Likewise, the skeletal density remained relatively unchanged.
The reduction in water content, pore volume and the changes in shrinkage behaviour under increasingly severe MTE conditions are
suggestive of the physical changes that accompany increased coalification (rank) within the lignitic range.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Lignite dewatering; Pore structure; Mercury intrusion porosimetry

1. Introduction

Mechanical/thermal dewatering (MTE) is a process

*
Corresponding author. Present address: Hitachi Power Europe,
Technology Center, Research & Development, Duisburger Strasse 375,
46049 Oberhausen, Germany. Tel.: +49 208 833 2948; fax: +49 208 833
872948.
E-mail address: c_bergins@hitachi-power.com (C. Bergins).
1
Present address: HRL Technology, 677 Springvale Road, Mulgrave,
Vic. 3170, Australia.
developed for the energy efficient removal of water from
high moisture content lignites utilised in power plant pro-
cesses. During the MTE process lignite is typically heated
to between 150 and 210 C and the water removed non-
evaporatively by the application of mechanical pressure.
In the first and second part of this series [1,2] the mecha-
nisms of water removal during the MTE process were

0016-2361/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2006.06.019
4 C. Bergins et al. / Fuel 86 (2007) 3–16

investigated and the process kinetics described by means of
a rheological model combining creep and consolidation
theory. This paper focuses on the effects of MTE on the
physical properties of low rank coals. Of particular interest
are the effects of MTE temperature and pressure on pore
structure, mercury surface area, apparent density and com-
pressibility as well as on shrinkage behaviour upon oven
drying. This will provide valuable information for the util-
isation of MTE products in current and new generation
power plants, and give an indication to their suitability
for the export market.
Currently, there is no clear understanding of the basic
parameters influencing the above described physical prop-
erties during the coalification process, despite some proper-
ties appearing to correlate with coal rank and carbon
content [3–7]. As studies undertaken by Chaffee et al. [8]
and Hulston et al. [9] have shown the chemical composition
of MTE treated coals remain relatively unchanged during
the MTE process, MTE treated coals provide an excellent
system for disentangling the effects of physical and chemi-
cal factors. In the early stages of coalification it is thought
that conditions can to some extent be mimicked by those
found during the MTE process [10], so that the effects of
processing conditions on physical properties will also shed
light on changes occurring during natural coalification [11].
The physical structure of dried porous materials, includ-
ing coal, can be characterised by a number of techniques,
including CO2 adsorption experiments and mercury intru-
sion porosimetry (MIP). Whereas CO2 gas adsorption pro-
vides information on the surface area, pore volume and
pore size distribution of pores in the micopore size region,
MIP provides similar information in the macro and meso-
pore size region. Numerous MIP studies on coal have been
undertaken since the first experiments of Zwietering and
van Krevelen [12], including detailed analyses of compress-
ibility [5,13], reintrusion and retention of mercury [14], and
pore volume and mercury surface area determinations for
coals of different rank and location [4–7,15].
2. Experiments
A detailed description of the MTE dewatering device
and experimental procedure used is provided by Bergins
[1,2]. In brief, 100 g of raw coal was added to the MTE cell,
to which was added 100 g of deionised water to form a coal
water slurry. The slurry was then dewatered via the appli-
cation of temperatures up to 235 C and pressures up to
12 MPa. Upon completion of the MTE run, a filter cake
was formed with a diameter of 70 mm and a height of
between 10 and 35 mm, depending upon the experimental
conditions used.
Investigations were carried out on three coals from Aus-
tralia, Greece and Germany (Table 1). Whereas the Austra-
lian coal had a high moisture, but low ash content, the
Greek coal had high levels of both moisture and ash. The
German coal had a slightly lower moisture content, with
ash level between those of the other two coals.
2.1. Moisture content determination
The moisture content was determined based on a
method similar to the DIN 51718 standard [16]. Since the
shrinkage behaviour of samples was being investigated,
whole pellets were dried in an air atmosphere at 105 C
for 48 h to ensure complete moisture removal. The oven
dried MTE products were subsequently used for helium
density and mercury intrusion porosimetry experiments.
2.2. Helium density determination
The helium density, qHe, was determined by helium pyc-
nometry using an AccuPyc 1330 (Micromeritics, Norcross,
GA, USA) Pycnometer. The unit was calibrated on a daily
basis and measurements were carried out on oven dried
1.5–2.5 g sub-samples. Prior to taking measurements, sam-
ples were purged with helium 99 times to ensure complete
removal of adsorbed gases. The helium density was deter-
mined from an average of 10 measurements.
2.3. Ultimate and proximate analysis
Ultimate and proximate analysis was done by HRL
Technology Pty. Ltd. (Melbourne). Carbon, hydrogen
and nitrogen levels were determined on a Leco CHN600
analyser, while ash yields were measured on a Leco
MAC400 analyser. Total sulphur levels were determined

Table 1
Properties of raw coals investigated
Country Open cut Water Water Ash yield He density Calorific value
(wt%, wb) (g/g, db) (wt%, db) (g/cm3) (MJ/kg daf)
Australia Loy Yang (Latrobe Valley) 60.8 1.55 1.0 1.393 26.7
Greece Ptolemais 60.4 1.53 14.1 1.517 n/a
Germany Hambach (Rhineland) 53.1 1.13 6.3 1.444 26.6
Country Volatile matter Fixed carbon C H N Stotal Odiff
(% daf) (% daf) (wt%, daf) (wt%, daf) (wt%, daf) (wt%, daf) (wt%, daf)
±0.7 ±0.7 ±1.3% ±0.12% ±0.1% ±0.05% ±0.14%
Australia 52.5 47.6 68.2 4.70 0.51 0.30 26.3
Greece 57.7 42.3 62.7 4.99 1.57 0.76 30.0
Germany 54.6 45.4 66.7 4.93 0.77 0.43 27.2
 C. Bergins et al. / Fuel 86 (2007) 3–16 5

using an inductively-coupled plasma-optical emission spec- 1 1

V micro ¼  ½cm3 =g ð5Þ
trometer (ICP-OES). qskeletal qHe
When expressing intrusion volumes on a dry and ash free
2.4. Mercury intrusion porosimetry
basis, calculations were based on the mean values of the
ash yields and helium densities (Table 1). The density of
Pore size measurements were obtained by mercury intru-
the mineral matter was taken as 2.7 g/cm3 [4].
sion porosimetry (MIP), using an AUTOPORE II 9220
Pore size distributions were calculated from the com-
mercury porosimeter (Micromeritics). The instrument is
pressibility corrected intrusion data as logarithmic differen-
capable of applying pressures p between 3.4 kPa and
tial intrusions
414 MPa, which, according to the Washburn equation for
cylindrical pores [17], V iþ1  V i
LDI ¼ ½cm3 =g ð6Þ
log d i  log d iþ1
2r cos h 4r cos h
p¼ ¼ ½Pa ð1Þ
r d after interpolating the 240 experimental data points to 80
equates to a pore diameter d range of 0.0036–437 lm at a diameters, which were equally spaced in the logarithmic
surface tension r of 0.485 N m1 and a contact angle h of scale. Using the corrected MIP data, the surface area A
140 [6,14,17]. Experiments were carried out in 3 cm3 cali- (from the work of wetting)
Pd i ¼0:0036 lm
brated powder and solid penetrometers using about 0.5 g d i ¼50 lm pi DV i
of oven dried MTE product with a diameter of 2–10 mm. A¼ ½m2  ð7Þ
r cos H
All experimental data was corrected for mercury compress-
ibility and penetrometer deformation by subtracting results and mean pore diameters dmean (by volume)
!
from blank runs performed on empty penetrometers. All 1 i X
d ¼0:0036 lm

results are expressed either on a volume per gram dry coal d mean ¼ d V ¼ Vi ð8Þ
2 d ¼50 lm
basis (db) or on a dry and ash free basis (daf). i

During the course of an experiment, both the intruded could be calculated. To avoid errors introduced by inter-
and extruded mercury volumes were determined. This particle void filling at the beginning of an MIP experiment,
allowed the compressibility j of the coal matrix to be deter- the surface area and mean pore diameter calculations were
mined from the slopes of either a cumulative intrusion vol- based on intrusion data collected in the macro and meso-
ume versus intrusion (compression, ji) pressure graph, or pore size regions.
from a cumulative extrusion volume versus extrusion
(decompression, je) pressure graph 2.5. Pore volume and shrinkage determination
 
1 oV  oV mercury =msample  1
j¼ ¼ q  ½Pa  ð2Þ As part of this investigation, the pore volume of both
V op  T
He
op T
wet and oven dried MTE filter cakes were determined. This
For reasons described in more detail in Section 3.1, the allowed the effect of the MTE process and oven drying on
compressibility correction for the coal matrix was based pellet shrinkage to be determined.
on the slope of the extrusion, rather than intrusion data The pore volume V wet
pore
pellet
of wet MTE filter cakes was
j determined from the difference between the total pellet
V corrected ¼Vi p ½cm3 =g ð3Þ
i
qHe i volume (determined from caliper measurements) and the
volume occupied by the coal, such that
The extrusion was measured down to at least 0.21 MPa
(d = 7 lm), up to which point the extrusion curve was p mcoal
V wet
pore
pellet
¼ D2wet H wet  ¼ V water þ V gas ð9Þ
parallel to the intrusion curve. The percentage of retained 4 qHe
mercury upon extrusion could therefore be calculated via
where Dwet and Hwet represent the diameter and height of
the following relationship:
the wet pellet, and m and qHe the mass and helium density
V extrusion
7 lm  V intrusion
7 lm of the dry coal respectively. It should be pointed out that
R¼  100 ½% ð4Þ while the pores are predominantly filled with water, Vwater,
V intrusion intrusion
0:0036 lm  V 7 lm
they contain a small amount of gas, Vgas, which is pro-
The inter/intra particle boundary was taken as d = 50 lm. duced during thermal dewatering or introduced when the
The macropore volume (Vmacro) and mesopore volume pellet expands upon release of the applied pressure after
(Vmeso) were taken as the total volumes with diameters the MTE process [18].
ranging between 0.05 and 50 lm and 0.0036 and 0.05 lm The total pore volume V dry pore
pellet
of oven dried MTE
respectively. products was determined by two methods. In the first
The micropore volume (Vmicro) was calculated from the method the pore volume was taken as the sum of
skeletal density (calculated from maximum mercury intru- the macro, meso and micropore volumes as determined
sion after compressibility correction) and the He density from MIP experiments. The second method involved tak-
(Fig. 6), ing the difference between the total dry pellet volume
6 C. Bergins et al. / Fuel 86 (2007) 3–16

(determined from calliper measurements, ±0.1 mm) and
the volume occupied by the coal, such that
p mcoal
V dry
pore
pellet
¼ D2dry H dry  ð10Þ
4 qHe
where Ddry and Hdry represent the diameter and height
respectively of the dry pellet. The pellet shrinkage was then
determined from the difference between the wet and dry
pore volumes.
3. Results
Shown in Fig. 1 are the effects of MTE temperature (T)
and pressure (pS) on the moisture content of the Austra-
lian, Greek and German coals. For all three coal types
the moisture content decreased almost linearly with
increasing temperature up to about 180 C. As a function
of pressure, the moisture content decreased significantly
up to an applied pressure of about 5 MPa, beyond which
further increases in pressure resulted in only slight reduc-
tions in moisture content. The kinetic behaviour of this
process is described in more detail by Bergins [1].
Since the pores are almost entirely filled with water
(though they do contain a little gas [1,18]), the changes in
total pore volume of the wet MTE product will follow
the same trends with MTE temperature and pressure as
the moisture content. However, this relationship does not
give any information on how the pore size distribution var-
ies with MTE conditions. To investigate the porosity of
MTE treated coals (Fig. 1) in more detail, samples were
characterised by mercury intrusion porosimetry (MIP).
The advantage of this technique is that it allows pore size
distributions (PSD) to be easily determined over a broad
pore size range, spanning several orders of magnitude.
The technique is however limited, in that samples need to
be completely dry, thus allowing porosity and pore size dis-
tribution data only to be obtained for oven dried MTE
products, which are known to have undergone shrinkage
[19,20]. However, as the pore volume of the wet MTE
product is known, the pore volume measured by MIP
can be used to determined the degree of shrinkage during
oven drying, an important parameter in itself and a useful
index of physico-chemical changes occurring during the
MTE process. A more detailed analysis is provided later.
Furthermore, care must be taken when interpreting the
lower mesopore diameter range, as the high intrusion pres-
sures required to measure pore sizes in this region may lead
to sample compression or degradation [13,14]. This would
lead to an overestimation of the total intrusion volume,
resulting in an underestimation of the micropore volume
and an overestimation of the skeletal density. Such an over-
estimation of the skeletal density was indeed observed in
this study, where MIP determined skeletal densities (uncor-
rected) were found to be higher than helium densities
(Fig. 6a). This trend is unexpected as the MIP technique
is only capable of measuring pore diameters down to
3.6 nm, compared to 0.16 nm for a helium atom, thus sug-
gesting that sample compression is occurring.
To establish the significance of sample compression for
the low rank coals investigated in this study, compressibil-
ity values were determined for all MTE products.
3.1. Correction of PSD curves for compression effects
Shown in Fig. 2a are cumulative intrusion curves for the
Australian coal, which show a sequential decrease in intru-
sion volume with increasing MTE temperature at a con-
stant applied pressure of 5 MPa. Fig. 2b shows the same
data, with the applied pressure axis as a linear rather than
logarithmic scale, to highlight the high-pressure region of
the curves. To assist in distinguishing the different experi-
mental conditions from each other, each temperature data
set has been offset such that the maximum cumulative
intrusion volume obtained for each experiment differs by
0.015 cm3/g. In addition, a linear regression has been fitted
to the high pressure region of each intrusion (dash-dotted
line) and extrusion (dashed) data set, from which the sam-
ple compressibility (i.e. ji and je) could be determined

1.2 1.75
T [˚C] 25 ºC T [˚C] 25 ºC T [˚C] 25 ºC
p = 5MPa
S 85 ºC 85 ºC 85 ºC
1.50
1.0 145 ºC 145 ºC 145 ºC
Water content [g/g] (db.)

1.25 205 ºC 205 ºC 205 ºC

0.8 raw raw raw
1.00
0.6
0.75
0.4
0.50
Australia
0.2 Greece 0.25
Germany
Australia Greece Germany
0.0 0.00
0 50 100 150 200 250 0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
Temperature T [ºC] Pressure p [MPa] Pressure p [MPa] Pressure pS [MPa]
S S

Fig. 1. Effect of MTE temperature and pressure on the water content of Australian, Greek and German coal [18].
 C. Bergins et al. / Fuel 86 (2007) 3–16 7

(a) Pore diameter [μm] (b) Pore diameter [nm] (c) Pressure [MPa]
100 10 1 0.1 0.01 64 16 8 6 5 4 3 0.01 0.1 1 10 100
0.55 0.8
Australia p =5 MPa meso
0.50 T [ºC] S macro pores

Log differential intrusion [cm3g–1]

0.7 pores
Cumulative intrusion [cm3g–1]

Cumulative intrusion [cm3g–1]

0.45 25
85 0.6
0.40
145
on
0.35 205
ext rusi 0.5
235
0.30 n
ru sio 0.4 0
0.25 int
0.20 0.3 0

0.15

0.015
0.2 0
0.10 raw data
raw data 0.1 0
0.05 intrusion fit intrusion corr.
extrusion fit extrusion corr.
0.00 0.0 0
0.01 0.1 1 10 100 0 100 200 300 400 500 100 10 1 0.1 0.01
Pressure [MPa] Pressure [MPa] Pore diameter [μm]

Fig. 2. (a) Cumulative intrusion and extrusion of mercury, (b) fitting of regression lines for compressibility determination and (c) compressibility corrected
pore size distribution curves for Australian MTE treated lignite.

according to Eq. (2). The corresponding pore size distribu- linear over a generally broader pressure region, ranging
tions, expressed as a log differential intrusion, are shown in between 200 and 400 MPa.
Fig. 2c. For each data set, the compressibility corrected Figs. 2b and 3a (left) clearly show hysteresis behaviour
data points determined from mercury intrusion (dash-dot- between mercury intrusion and extrusion data, which is
ted line) and extrusion (dashed line) data have been particularly evident in the high pressure region. The degree
included. For ease of interpretation the baseline for each of hysteresis increases with increasing MTE temperature,
temperature data set has been offset by 0.1 cm3/g. which is associated with an increase in intrusion slope, with
The mercury intrusion curves in Fig. 2b show a contin- the extrusion slope remaining constant. This results in a
uously changing slope, with a narrow linear region in the constant je and an increasing ji value with increasing
300–400 MPa pressure range, from which the intrusion MTE temperature. Similar trends in compressibility behav-
compressibility, ji, was calculated. The linear behaviour iour are seen for the Greek (Fig. 3, center) and German
reported by other researchers [6,15] for lignites and sub- (Fig. 3, right) coals. The increase in ji with MTE tempera-
bituminous coals at intrusion pressures as low as 100– ture is somewhat unexpected, since the compressibility of
200 MPa was not apparent. This may be due to the higher the skeletal coal structure is a physical constant which
intrusion pressures used in this study (414 MPa), causing changes only slightly (30%) with increasing rank and
the slope at lower intrusion pressures to become more obvi- chemical composition [3]. The fact that different compress-
ous relative to other studies, which only used pressures up ibilities are calculated from mercury intrusion and extru-
to 207 MPa. In comparison, the extrusion compressibility, sion data indicates that different processes are occurring
je, was obtained from mercury extrusion data, which was during the mercury intrusion and extrusion process.

25
(a) intrusion, κ i pS=1 MPa pS=5 MPa raw
2 MPa 7 MPa
20
3 MPa 10 MPa
Pa ] (daf.)

15
–1

10
–11

5
κ [10

15
(b) extrusion, κ e
10

5 Australia Greece Germany

0 50 100 150 200 0 50 100 150 200 0 50 100 150 200 250
Temperature T [ºC] Temperature T [ºC] Temperature T [ºC]

Fig. 3. Compressibilities of the three coals determined from (a) mercury intrusion and (b) mercury extrusion data.
8 C. Bergins et al. / Fuel 86 (2007) 3–16

solid-solid contact points

(after dewatering, shrinkage)

1) small pores (not

accessible to MIP)
2
2) ‘bottle neck’pores
1 which retain mercury
after intrusion
1

porous network compression

and deformation

coal skeleton compression

Fig. 4. Scales of compression and deformation.

Hysteresis is commonly associated with mercury reten-
tion and has been ascribed to a number of factors, includ-
ing the ‘ink-bottle’ effect, which appears as a breakage of
the mercury column in a narrow neck as a result of non-
steady capillary pressure [14,17] (Fig. 4). Other reasons
for mercury retention include contact angle hysteresis in
conical pores [14,17], irreversible sample destruction and
reversible sample compression [13].
The increase in hysteresis with increasing MTE temper-
ature is difficult to explain in terms of changes in ‘ink-bot-
tle’ effect or contact angle hysteresis, because there are no
plausible mechanisms for changes in these quantities with
MTE temperature. The increase in hysteresis may, how-
ever, be rationalised in terms of an increase in sample
compression during mercury intrusion, including both the
compression of pores as well as the skeletal coal structure
(Fig. 4). Pore volume compression effects could be caused
by a shift in pore size distribution from larger to smaller
sized pores, as well as an increase in the number of ‘closed’
pores and pores which are too small for mercury to intrude
into. A shift in pore size distribution with increasing MTE
temperature is evident from Fig. 2c (also see Figs. 9 and
10), which shows an increase in mesopore volume and an
associated decrease in macropore volume and mean pore
diameter at progressively higher MTE temperatures. This
would result in a more compressible coal structure, where
empty meso- and micropores (and possibly closed pores)
experience increased compressive forces during the mer-
rise in the measured ji value. Unfortunately, the effects
of pore filling and sample compression are not easily sepa-
rated [15]. For this reason, the compression effects on pores
and skeletal coal structure can also not be separated [21].
Consequently, while compressibility values for pore size
distribution corrections are commonly determined from
mercury intrusion data, this approach is not valid for the
coal samples used in this study.
In comparison, the more constant linear relationship
seen for mercury extrusion experiments, suggests that only
elastic deformations are occurring, where at high extrusion
pressures, pore emptying occurs primarily due to the re-
expansion (i.e. decompression) of the coal structure. This
results in consistent compressibility behaviour with increas-
ing MTE temperature (Fig. 3b). Similar small changes in
coal compressibility were seen by Schuyer et al. [3], who
used sound velocity measurements to determine the com-
pressibility for a range of coal ranks with carbon values
ranging between 82% and 90%.
It is interesting to note that while the degree of hysteresis
in the mesopore diameter region increases with increasing
MTE temperature (Fig. 2b), the percent mercury retained
(relative to maximum intrusion volume) upon extrusion
remains relatively constant at about 45% at MTE temper-
atures up to about 200 C (Fig. 5). This suggests that at
60
Percentage mercury retention [%]

cury filling of macropores and larger mesopores (Fig. 4). 50

Compression of the skeletal coal structure in turn is
expected to become significant at higher intrusion pres- 40
p =1 MPa
sures, particularly in the mesopore diameter range. This S
30 2 MPa
effect is however expected to decrease at very high MIP 3 MPa
pressures due to an increase in the number of contact 20 5 MPa
points in the compressed network, causing the resistance 7 MPa
against further compression (Fig. 4) to increase. 10 10 MPa
raw Australia
For all three coal samples, the results therefore suggest 0
that the non-linear intrusion-pressure curve (and hence 0 50 100 150 200 250
hysteresis) is due to the combined effects of pore filling Temperature T [ºC]
and sample compression [15]. This effect is enhanced with Fig. 5. Percent mercury retention at the end of MIP experiments for
increasing MTE temperature, consequently leading to a Australian coal.

high MTE temperatures, the increased relative volume dif-
ference between mercury intrusion and extrusion at high
mercury pressures is compensated for by higher extrusion
volumes (i.e. higher gradients) once lower mercury extru-
sion pressures (e.g. 10 MPa) have been reached. This
behaviour is thought to result from the reordering of the
macromolecular network structure [13], suggesting a
reversible deformation of the coal network structure. This
result also indicates that an increase in irreversible pore
structure destruction during MIP experiments for these
samples is unlikely. This is in agreement with the work of
Spitzer [23], who observed no sample destruction for
MIP pressures up to 100 MPa.
The results suggest that the use of compressibility values
derived from mercury extrusion data is a more appropriate
method for correcting pore size distribution data. This is
further supported by the fact that the use of compressibility
values determined from mercury intrusion data, results in
zero differential intrusion in the higher pressure regime
(Fig. 2c, dash-dotted lines) and an underestimation of the
mesopore volume. In addition, it would result in positive
intrusion during depressurisation, which is physically not
possible. Furthermore, without compressibility correction,
the total intrusion volume is overestimated (due to com-
pression of pores and the skeletal coal structure at higher
intrusion pressures), resulting in an underestimation of
the micropore volume and thus an overestimation of the
skeletal density. This is more clearly illustrated in Fig. 6a,
where the average helium densities are lower relative to
uncorrected MIP determined skeletal densities. However,
upon correction (Fig. 6b), the He densities are sensibly
higher than the MIP determined skeletal densities. Based
on these findings, it was decided to use compressibility val-
ues derived from mercury extrusion data for all pore size
distribution corrections (Fig. 2c, dashed lines).
It is interesting to note that MTE pressure had relatively
little effect on compressibility (je) (Fig. 3). This can be
explained by the fact that MTE pressure had little influence
on the mesopore or micropore volume (Fig. 9).
1.5
(a) calculated from raw data
1.45
He
1.4
1.35
MIP
1.5
(b) calculated from corrected data
[g/cm3] daf.
1.45
1.4
1.35
Australia
0 50 100 150
Temperature T [ºC]
Fig. 6. Skeletal densities calculated from mercury intrusion at maximum pressure (with and without correction for compressibility) and He densities. The
range of helium density results are represented by the hatched region for ease of interpretation. There is a higher degree of scattering for the German and
Greek coals due to their higher ash content, which in part is present as discrete minerals.
C. Bergins et al. / Fuel 86 (2007) 3–16 9
3.2. Coal compressibility
Based on mercury extrusion data, the calculated com-
pressibility determined for all three coal samples was unaf-
fected by MTE temperature or pressure (Fig. 3). The range
of compressibility values (0.6 · 1010–2.2 · 1010 Pa1)
obtained in this study cover the whole range of values given
in the literature for coals with carbon contents between
65% and 95% [5,6,12,13]. Several authors have drawn cor-
relations between compressibility and carbon content, and
showed the compressibility to initially decrease with
increasing carbon content and subsequently increase at
higher carbon concentrations [5,6]. No such correlations
could be drawn in this study as the change in carbon con-
tent of the samples remained below 2% at the highest MTE
temperature (230 C) investigated [18]. The results from
mercury intrusion porosimetry however suggest that, irre-
spective of the carbon content, the compressibility value
can be influenced by the porosity and pore size distribution
of the sample. This possibly explains why investigations of
coals from different countries or open cuts result in differ-
ent compressibility curves when plotted only as a function
of carbon content (compare [6]).
This is also in accordance with the finding of Teichmül-
ler who argued that ‘the water content of the lignite stage is
a far better measure of the degree of coalification than the
carbon content or content of volatiles’ [11].
3.3. Skeletal density
The skeletal density (corrected for compression effects
determined from mercury extrusion data) for all three coal
types remained relatively constant with increasing MTE
temperature and pressure. This is to be expected as the
MTE process has relatively little effect on the chemical
composition of the coals [22]. Values tended to range
between about 1.35 and 1.40 g/cm3 for the Australian
and German coals and 1.30 and 1.45 g/cm3 for the Greek
coal.
pS=1 MPa pS=5 MPa raw
2 MPa 7 MPa
3 MPa 10 MPa
Greece Germany
200 0 50 100 150 200 0 50 100 150 200 250
Temperature T [ºC] Temperature T [ºC]
10 C. Bergins et al. / Fuel 86 (2007) 3–16

3.4. Pore size distribution decreases the total pore volume (including a small amount
of gas) [22] of all three coal types. Upon oven drying, the
Shown in Fig. 7 is the effect of MTE temperature on the MTE products shrink (discussed later), resulting in further
pore size distribution of all three coal types treated at a pore volume loss, such that the pore size distributions
constant mechanical pressure of 5 MPa. The corresponding shown in Fig. 8 are the result of both the MTE process
effects of MTE pressure for four different temperatures are and shrinkage upon oven drying.
shown in Fig. 8. All results have been expressed as logarith- As illustrated in Fig. 8 most of the pore volume for the
mic differential intrusion curves, where the intrusion vol- Australian coal treated under mild MTE processing condi-
umes have been corrected (using je) for compressibility tions is in the macropore size region, with a peak volume at
effects. Furthermore, for each condition, the baseline has a pore diameter of about 0.4 lm. Increasing the MTE pro-
been offset by 0.05 cm3/g, where the dashed lines (marked cessing temperature and pressure caused the distribution to
with corresponding symbols) represent the actual zero line flatten and shift to smaller diameter pores. The correspond-
for each experiment. For ease of interpretation, the pore ing mean pore diameter results in Fig. 10 show this effect to
size distributions have been divided into macro and meso- be more strongly influenced by temperature than pressure.
pore size regions, where the inter/intra particle boundary Furthermore, Fig. 9 shows the shift in pore size distribu-
has been set at 50 lm. To allow easy comparisons to be tion to be associated with a decrease in macropore volume
made between different coal types and processing condi- and an increase in mesopore volume with increasing MTE
tions, the individual macro and mesopore volumes, as well temperature. This finding supports the idea that larger
as calculated micropore and total pore volumes have been pores are being deformed during MTE dewatering, result-
shown in Fig. 9a–d. Additionally, the mean pore diameter ing in an increasing number of smaller pores. Both the
and specific mercury surface areas determined from the macropore and mesopore volumes decreased with increas-
pore size distributions are shown in Figs. 10 and 11 respec- ing MTE pressure (Fig. 9a and b). The micropore volume
tively. It should be noted that the surface areas calculated in turn was relatively unaffected by increases in MTE tem-
according to Eq. (7) have been corrected for compression perature and pressure (Fig. 9c). Despite a decrease in mac-
effects, based on compressibility values derived from mer- ropore volume and an increase in mesopore volume, the
cury extrusion data. Furthermore, the calculated surface total pore volume decreased with increasing MTE temper-
areas are only valid for pores intruded by mercury (i.e. ature (Fig. 9d). This is consistent with the decreased mois-
3.6 nm to 50 lm). No assumptions concerning the pore ture content results shown in Fig. 1. Similar decreases in
geometry are included in Eq. (7) since only the mechanical total pore volume occurred as a function of increasing
work of wetting the coal surface is calculated – even if the MTE pressure.
calculation of surface areas from the filling of cylindrical The shift from macropores to mesopores with increasing
pores would lead to the same equation. Also the error of MTE temperature is associated with an increase in MIP
compressibility correction seems negligible, since the same determined surface area (Fig. 11). The reverse trend is seen
trends with slightly higher or lower absolute values result with increasing pressure, due to the resultant decrease in
from calculations which have been performed without mesopore volume. In comparison, surface areas determined
any correction or with a correction using the compressibil- for Loy Yang Low Ash MTE products by CO2 adsorption
ity calculated from the intrusion curve. measurements, were about 20% higher and remained
As indicated by the water content values shown in unchanged with MTE temperature and pressure [20]. These
Fig. 1, increasing the MTE processing severity significantly differences are due to the MIP method measuring the

T [ºC] p =5 MPa T [ºC] p =5 MPa T [ºC] p =5 MPa

25 145 S 25 145 S 25 145 S
Log differential intrusion [cm3 g –1]

0.60 55 175 Australia 55 175 Greece 55 175 Germany

85 205 (a) 85 205 (b) 85 205 (c)
0.50 115 235 115 235 115 235
macro pores meso
pores
0.40
0 0 0
0.30 0 0 0
0 0 0
0.20 0 0 0
0 0 0
0.10 0 0 0
0 0 0
0.00 0 0 0
100 10 1 0.1 0.01 100 10 1 0.1 0.01 100 10 1 0.1 0.01
Pore diameter d [μm] Pore diameter d [μm] Pore diameter d [μm]

Fig. 7. Effect of MTE temperature on the logarithmic differential intrusion of (a) Australian, (b) Greek and (c) German coals.
influence of larger sized pores (3.6 nm to 50 lm diameter), Under mild MTE processing conditions, the total poros-
while the CO2 adsorption method accounts for smaller sized
pores (0.16–2 nm diameter), which dominate the surface
area of a substance and which remain relatively unaffected
by MTE temperature and pressure.
It should be noted that surface areas obtained from the
MIP method are more useful for describing dewatering
trends, as most of the water is entrained in macro and mes-
opores, rather than micropores. In comparison to other
researchers, surface areas calculated in this work are about
3–10 times higher than values quoted in the literature
[12,23]. This is most likely due to the higher mercury intru-
sion pressures used in this work, leading to an increased
surface area contribution from smaller sized pores.
It is interesting to note that at 5 MPa, the increases in
mesopore volume (Fig. 9b) and surface area (Fig. 11),
began to reverse at elevated temperatures (>205 C). This
is possibly due to the onset of thermal decomposition, lead-
ing to chemical changes [9,18,20] similar to those observed
during natural coalification. In addition, there may be
some melting of waxes, which can block access of mercury
to parts of the pore system once the coal is highly com-
pressed. Decreases in mesopore volume and surface area
were also seen with increasing MTE pressure, again indi-
cating the possible blockage of pores to mercury intrusion.
12 C. Bergins et al. / Fuel 86 (2007) 3–16

Australia Greece Germany

0.6 (a) macro pore volume
0.5 p =1 MPa p =7 MPa
S S
2 MPa 10 MPa
0.4 3 MPa raw
0.3 5 MPa
0.2
0.1
0.0
0.12 (b) meso pore volume
pore volume [cm3/g]

0.09 Australia Greece Germany

0.06
0.03
0.00
0.06 (c) micro pore volume
0.03
0.00
0.6 (d) total pore volume
pS=1 MPa pS=7 MPa
0.5 2 MPa 10 MPa
3 MPa raw
0.4 5 MPa
0.3
0.2
0.1
0.0
0 50 100 150 200 0 50 100 150 200 0 50 100 150 200 250
Temperature T [ºC] Temperature T [ºC] Temperature T [ºC]

Fig. 9. Macro, meso and micropore volume (dashed line for micropore volume gives maximum deviation for correction using the intrusion compressibility
ji) and total pore volume for all dried samples.

(a) (b) (c)

Mean pore diameter dmean [μm]

0
10
p =1 MPa
S
2 MPa
3 MPa
1 5 MPa
10
7 MPa
10 MPa
raw
Australia Greece Germany
2
10
0 50 100 150 200 0 50 100 150 200 0 50 100 150 200 250
Temperature T [ºC] Temperature T [ºC] Temperature T [ºC]

Fig. 10. Mean pore diameter calculated from MIP data.

The observed increase in mesopore volume, particularly temperature. This latter hypothesis is further supported
for the Greek coal, with increasing MTE temperature by the fact that no increase in mesopore volume was seen
could be due to a number of factors, including the genera- with increasing MTE pressure. To investigate this effect
tion of pores during the MTE process. However, this mech- further, the shrinkage behaviour of all three coal types
anism is unlikely considering that thermal dewatering starts was monitored as a function of increasing MTE tempera-
at about 140 C, leading to a collapse of the coal structure ture and pressure.
due to water release. As the water content of all coals is of
the same order of magnitude for constant MTE process 3.5. Shrinkage
parameters, the data suggests that the increase in mesopore
volume is more likely due to a ‘hardening’ of the coal struc- Shown in Fig. 12 is a comparison of the total pore vol-
ture, leading to changes in shrinkage behaviour (during ume of oven dried MTE products measured by MIP and
drying prior to MIP measurements) with increasing MTE the direct measurement of pellet dimensions using callipers.
 C. Bergins et al. / Fuel 86 (2007) 3–16 13

45
p =1 MPa

Mercury surface area A [m2 g –1]

40 S
2 MPa
35 3 MPa
30 5 MPa
7 MPa
25 10 MPa
raw
20
15
10
5 Australia Greece Germany
(a) (b) (c)
0
0 50 100 150 200 0 50 100 150 200 0 50 100 150 200 250
Temperature T [ºC] Temperature T [ºC] Temperature T [ºC]

Fig. 11. Specific surface area calculated from MIP data.

macro pore limit 420 μm

the percentage shrinkage (difference relative to the total wet
1.0 pS=1 MPa
Dry pore volume (by MIP) [cm3/g]

0.8
0.6
0.4
0.2
0.0
0.0
Dry pore volume (by pellet dimensions) [cm3/g]
Fig. 12. Comparison of total pore volumes of dry MTE pellets measured
by MIP and calculated from pellet dimensions.
As illustrated, the pore volume from calliper measurements
is significantly higher, with the effect becoming more pro-
nounced at higher dry pore volumes. This is believed to
be due to the presence of cracks formed upon oven drying,
which are not being captured by the MIP technique, even if
the maximum pore volume is set to 420 lm, which corre-
sponds to the minimum pressure applied during MIP
measurements.
Since crack formation is dependent upon temperature,
which affects the binding strength as is commonly seen
for briquettes, all shrinkage data was calculated using dry
pore volumes determined from MIP measurements with
an inter/intra particle cut off diameter of 50 lm.
3.5.1. Effect of temperature on shrinkage
Shown in Fig. 13a is the effect of MTE temperature on
the dry pore volume of all three coal types, plotted as a
function of the total wet pore volume, determined from
wet pellet dimensions. Since crack formation occurs in
the later stages of drying, the error in the total wet pore
volume can be neglected. The corresponding volume differ-
ence between wet and oven dried MTE products, as well as
2 MPa
macro pore limit 50 μm pore volume) are shown in Fig. 13b and c respectively.
3 MPa At a constant applied MTE pressure of 5 MPa, the dry
5 MPa pore volume of the Australian coal decreased continuously
7 MPa with increasing MTE temperature. In comparison, while
10 MPa
values for the German coal remained relatively constant,
dry pore volumes for the Greek coal increased at elevated
MTE temperatures. The corresponding percentage shrink-
age results in Fig. 13c indicate, particularly for the Greek
and German coals, a decrease in shrinkage at temperatures
above about 85 C. Thus, indicating that a hardening of
Australia
the coal structure is indeed occurring at elevated MTE tem-
0.2 0.4 0.6 0.8 1.0 peratures. For the Australian similar behaviour is seen at
various pressures (see below), although the effect is not as
pronounced.
Coal hardening, and consequent porosity retention at
elevated temperatures, was also observed by Bongers
et al. [24], who investigated the effects of steam drying on
the pore structure of Loy Yang coal. Bongers et al.
observed that the use of steam drying at elevated tempera-
tures (e.g. 182–225 C) with a low degree of superheat,
resulted in little moisture loss, leading to the retention of
much of the bed moist porosity upon oven drying at
105 C. Bongers et al. argued that this effect was due to
cross-linking reactions occurring, where pore collapse was
prevented by the presence of water inside the pores.
The conditions experienced by the coal during the first
stages of the MTE process, when applied pressures are still
low and thermal dewatering occurs [1,25], are very similar
to those of the low superheat steam experiments carried out
by Bongers et al. It is thus feasible that similar cross-linking
reactions are occurring during the MTE process and give
rise to the observed resistance to shrinkage.
3.5.2. Effect of pressure on shrinkage
The effects of MTE pressure on the dry pore volume,
absolute volume reduction and percent shrinkage for all
three MTE treated coal types are shown in Fig. 14a–c.
For the Australian coal an increase in pressure led to a
reduction in the dry pore volume, indicating an increase
14 C. Bergins et al. / Fuel 86 (2007) 3–16

Dry pore volume [cm3/g]

0.6 (a) Australia Greece Germany

shrinkage
0.5
0.4
0.3 (T)
(T)
0.2
(T)
0.1
0
1.4 (b)
Shrinkage [cm3/g]

1.2
1
(T)
0.8 (T)
0.6 (T)
0.4
0.2
0
90 (c)
Shrinkage [%]

80 (T)
(T)
70 (T)
60
25 115 205
50 T[ºC]
55 145 235
(ps=5 MPa) 85 175 raw
40
0 0.25 0.5 0.75 1 1.25 1.5 0 0.25 0.5 0.75 1 1.25 1.5 0 0.25 0.5 0.75 1 1.25 1.5
Total pore volume wet (calculated from wet pellet dimensions) [cm3/g]

Fig. 13. Total pore volume of wet and dry MTE pellets and shrinkage.
Dry pore volume [cm3/g]

0.6 (a) Australia Greece Germany

shrinkage

0.5
0.4 1MPa (p) (p) (T)
0.3 (p,T) (T)
0.2
10MPa
0.1
(T) (p,T) (p,T)
0
1.4 (b) T= 25 ºC
Shrinkage [cm3/g]

1.2 85 ºC
145 ºC
1 205 ºC
(T)
0.8 raw (T)
0.6 (T)
0.4
0.2 (p) (p)
(p)
0
90 (c) (p)* (p)
Shrinkage [%]

80
(T,p)
70
(T)
60 (T)
50
(p) (T) (T)
40
0 0.25 0.5 0.75 1 1.25 1.5 0 0.25 0.5 0.75 1 1.25 1.5 0 0.25 0.5 0.75 1 1.25 1.5
Total pore volume wet (calculated from wet pellet dimensions) [cm3/g]

Fig. 14. Total pore volume of wet and dry MTE pellets and shrinkage.

in shrinkage (relative to the original pellet volume) with shrinkage of MTE products with pressure could thus be
increased water removal. This trend was consistent for all associated with a shift from larger to smaller diameter pores
MTE temperatures investigated. Shrinkage studies under- (Fig. 10), which would increase the capillary forces acting
taken by Evans on raw Yallourn coal showed that due to on the coal structure during drying. While a similar shift
the action of capillary forces, shrinkage is mainly associated in pore size distribution is seen with increasing MTE tem-
with the removal of capillary and multilayer water rather perature (Fig. 10), the reverse trend in shrinkage (i.e.
than bulk water [26]. The observed increase in percentage decreased shrinkage with increasing MTE temperature,
 C. Bergins et al. / Fuel 86 (2007) 3–16
Fig. 14) is believed to be due to the dominating effects of
hardening of the coal structure above about 85 C.
For the German coal an increase in pressure at 85 and
145 C resulted in an initial decrease in dry pore volume
(Fig. 14), which at higher MTE pressures levelled out at
about 0.1 cm3/g. The corresponding percentage shrinkage
results (Fig. 14) show an initial slight increase in shrinkage
with increasing pressure (p) which, as for the Australian
coal, is believed to be due to a shift in porosity to smaller
(e.g. capillary/multilayer) diameter pores. At very high
MTE pressures the degree of shrinkage for the 145 C case
(squares) decreased (p)* again, suggesting that a minimum
achievable pore volume (i.e. 0.1 cm3/g) has been reached
under these conditions. This minimum appears to be pres-
ent for all three coals, and is consistent with the work of
Evans, who observed a zero differential shrinkage at a pore
volume of about 0.1 cm3/g [26]. At a MTE temperature of
205 C, the shrinkage remained relatively constant with
increasing pressure, which could be related to the harden-
ing of the coal structure at elevated temperatures.
In terms of pressure dependent shrinkage behaviour, the
Greek coal showed similar trends to the German coal, with
the exception that the initial increase in shrinkage at 145 C
was absent.
The results obtained so far suggest that differences in
pore size distribution between the three different coal types
result mainly from differences in shrinkage behaviour.
It is interesting to note that the percentage shrinkage of
the German and Greek coals is about twice that of the Aus-
tralian coal, despite the water contents of the MTE prod-
ucts being of the same order of magnitude for constant
MTE process parameters (Fig. 1). One explanation for this
behaviour could be the higher ash content and elevated
acid extractable Mg and Ca levels present in the Greek
and German coals [18]. These elements and other clay com-
ponents are known to undergo significant shrinkage and
swelling [27,28]. On the other hand, there could be differ-
ences in the origin of plant material and cell wall structure
contained within the amorphous phase of the coals.
3.6. Relationship of physico-chemical properties to
coalification
Several researchers [29–31] have investigated the effects
of temperature and pressure on the artificial coalification
of peat, cellulose and lignin, subsequent to early experi-
ments of this type carried out by Bergius in 1913 [32]. Inter-
estingly, the experimental apparatus employed by Rollins
et al. [33] for this purpose was remarkably similar to that
of the MTE dewatering device used in the present study.
Under relatively mild processing conditions, for example
125 C/30–38 MPa lithostatic pressure for 8 days [29], it
has been reported that physical changes, such as reduced
porosity, were particularly evident (although these were
not measured by MIP) [31,33].
Thus, the reduction in water content, pore volume and
the changes in shrinkage behaviour under increasingly
15
severe MTE conditions are suggestive of the physical
changes that accompany increased coalification (rank)
within the lignitic range [11]. Prior investigations have
shown that differences in chemical composition (C, H, N
and O) between MTE products are only slight [22].
4. Conclusions
The effects of MTE on the physical properties of low
rank coals, sourced from Australia, Greece and Germany
were investigated. Of particular interest were the effects
of MTE temperature and pressure on physical properties
such as pore size distribution, mean pore diameter, surface
area and shrinkage behaviour. These characteristics were
determined mainly from MIP measurements, carried out
in conjunction with helium pycnometry measurements.
Using MIP intrusion and extrusion data, compressibility
values could be derived, which were used to correct MIP
derived data for compression effects. To allow easy com-
parisons to be made between different MTE processing
conditions and coal types, the pore size distribution was
divided into macro, meso and micropore volumes.
An increase in MTE temperature and pressure signifi-
cantly reduced the moisture content and porosity of all
three coal types investigated. Upon oven drying the wet
MTE products, shrinkage occurred, the porosity trends
of which may not necessarily follow those seen for wet
MTE products. For instance, while the total dry pore vol-
ume for the oven dried Australian coal decreased with
increasing MTE temperature, the reverse was seen for the
Greek and German coals at low MTE pressures. For all
coals, this was associated with an increase in mesopore vol-
ume at elevated temperatures. The overall decrease in total
pore volume seen for the Australian coal was due to the
reduction in macropore volume being greater than the rel-
ative increase in mesopore volume. All three coals showed
a decrease in mean pore diameter, which was also associ-
ated with an increase in mercury surface area. The
increased pore volume retention is believed to be due to a
hardening of the coal structure with increasing MTE tem-
perature, resulting in decreased percentage shrinkage.
For all three coals, the macro and mesopore volume
decreased with increasing MTE pressure, causing the total
pore volume to decrease. The corresponding increase in
percentage shrinkage seen for the Australian and German
(at 145 C) MTE samples is believed to arise from an
increase in capillary forces, associated with a decrease in
the average pore diameter. The decrease in shrinkage at
higher pressures in turn is likely due to a limiting pore
volume being reached (0.1 cm3/g), due to the resistance
of the solid against further compression.
The results thus suggest that the pore volume of MTE
products is a complex function of process parameters,
shrinkage and coal hardening. Generally mechanical ther-
mal dewatering produces a very low porosity product coal
with a pore volume of less than 0.2 cm3/g for typical MTE
conditions (e.g. 200 C, 5 MPa).
16 C. Bergins et al. / Fuel 86 (2007) 3–16
The observed changes in physical properties appear to
be somewhat analogous to the physical changes that
accompany coalification, within the lignitic range, and
are believed to have important implications for coal reac-
tivity in terms of combustion, spontaneous combustion
and other reactions that are controlled by the diffusion of
gases into and out of pores.
Acknowledgements
The authors gratefully acknowledge the financial and
other support received for this research from the Coopera-
tive Research Centre (CRC) for Clean Power from Lignite,
which is established and supported under the Australian
Government’s Cooperative Research Centre Program.
The Rudolf-Chaudoire-Foundation and the University of
Dortmund are also acknowledged for their support
through a Research Fellowship. Many thanks go to Dr.
Marc Marshall and Yuli Artanto for their valuable
comments.
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